Process of making a pressure sensitive adhesive article

ABSTRACT

A process comprising solution interpolymerizing a pressuresensitive resin containing a monomer with an enolizable keto group, formulating the interpolymer solution with a chelate ester of orthotitanic acid to obtain a solution with stringiness index of less than 0.3 inches, and coating the solution on a substrate using a reverse roll coater or a gravure roll coater. The viscosity and flow properties of the solution are used advantageously in high-speed coating processes.

United States Patent [1 1 McKenna, Jr.

[4 1 Aug. 19, 1975 1 1 PROCESS OF MAKING A PRESSURE SENSITIVE ADHESIVE ARTICLE [75] Inventor: Lawrence W. McKenna, Jr.,

Wilbraham, Mass.

[73] Assignee: Monsanto Company, St. Louis, Mo.

[22] Filed: Apr. 9, 1973 [21] Appl. No.: 349,168

[52] U.S. Cl. 427/207; 260/31.2 N; 260/328 N; 260/336 UA; 260/8073 [51] Int. Cl. C09j 7/04; C081 15/40 Field of Search 117/122 PA, 122 PF, 122 P. 117/76 A, 68.5; 260/4295, 429 .1, 29.1 R,

32.8 N, 33.6 UA

[56] References Cited UNITED STATES PATENTS 2,720,468 10/1955 Shacklett 117/34 3,006,941 10/1961 Mudrak et al. 260/4295 X 3,051,593 8/1962 Gray et a1 260/429.5 X 3,057,753 10/1962 Blat'l. 260/4295 X 3,245,921 4/1966 Friihauf Ct 211. 260/4295 X 3.387.994 6/1968 Dunton et a1 260/4295 X 3,398,014 8/1968 Turner 117/111 3,415,762 12/1968 Block et a1 260/4295 X 3,467,610 9/1969 Fiarman et al.. 260/22 3,505,369 4/1970 Deffner 260/429 3,511,696 5/1970 Murray 117/111 3,532,708 10/1970 Blance 260/312 3,632,412 1/1972 Blance et a1. 117/122 X 3,720,562 3/1973 Drelich 117/161 X 3,740,366 6/1973 Sanderson et a1. 117/122 X 3,769,254 10/1973 Anderson et a1. 260/33.4

Primary E.\'aminerBernard D. Pianalto Attorney, Agent, or Firm-R. B. Blance; E. P. Grattan; J. C. Logomasini 1 1 ABSTRACT 6 Claims, N0 Drawings PROCESS OF MAKING A PRESSURE SENSITIVE ADHESIVE ARTICLE BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to organic solvent solutions containing chelate esters of orthotitanic acid and resins with functional groups capable of reaction with the esters. In another aspect, the invention relates to a process of manufacture of articles containing films of pressure-sensitive resin.

2. Description of the Prior Art Pressure-sensitive resins are used conventionally in the form of films to provide adhesive bonds between normally non-adhering superstrates and substrates. The films may be prepared by casting them from organic solvent solutions and evaporating the solvent.

Constraints are placed on the molecular weight of the pressure-sensitive resin by the viscosity of the solution necessary for ease of coating on commercial coating machines and by the solution concentration required for economical operation. In general, low solution viscosity and high solution concentration are desired in the pressure-sensitive resin solution, and, hence, a resin of relatively low molecular weight is preferred for film casting.

Once a bond has been made by a pressure-sensitive film placed between a substrate and a superstrate, the

pressure-sensitive film may be subjected to stress generated by the weight of the superstrate or by dimensional change in the substrate or superstrate caused by thermal expansion, stress relaxation, plasticizer migration or the like. In general, a high molecular weight and a high cohesive strength is desired in the pressuresensitive resin so that it may resist the stresses induced in the adhesive film. The opposing requirements of low molecular weight resin for ease of coating and high molccular weight resin for load holding ability are conventionally reconciled by the use of crosslinkable resin systems which can be applied at low molecular weight and cured to a high molecular weight. 1

Metal alkoxides are taught by Blance in US. Pat. No. 3,532,708 as crosslinking agents for solution pressuresensitive adhesives. They offer the potential of cure at room temperature merely by evaporation of the solvent. Of particular interest have been tetraalkyl titanates which are formulated with hydroxy pressuresensitive resins in alcohol solutions to yield stable solutions from which crosslinked pressure-sensitive resins are obtained by evaporation of the alcoholic solvent. However, such titanates particularly the lower alkyl titanates impart high solution viscosity and undesirable flow to the resin solutions.

The undesirable flow is manifested by the tendency of the resin solution to form a highly extended string or column of fluid when a spatula or like object is pulled rapidly out of the solution. Solutions exhibiting such stringiness are difficult to apply on modern high-speed coating machinery. Uneven splitting and transfer of the adhesive solution on the rolls causes uneven coating. On reverse roll coaters, the formation of strings at the roll nips produces a ribbed effect in the coating and on gravure rolls, webs of solution produce coating defects.

There is, therefore, a need in the art for pressuresensitive resin solutions with suitable viscosity and flow for application by coating rolls and which yield pressure-sensitive resins curable at room temperature or at slightly elevated temperatures to yield adequate cohesive strength.

SUMMARY OF THE INVENTION The above-mentioned need in the art is fulfilled by the present invention which provides pressure-sensitive resin solutions with improved viscosity and flow. The pressure-sensitive resin solutions comprise an organic solvent solution of:

1. an interpolymer having a weight average molecular weight in the range of 10,000 to 500,000 and a glass transition temperature in the range of 15 to 75C., the interpolymer comprising:

A. between 0.5 and 20 weight per cent of at least one monomer containing a hydroxyl, carboxyl or enolizable keto group,

B. at least one monomer selected from the group consisting of esters of acrylic acid and methacrylic acid containing from 6 to 20 carbon atoms, and

C. optionally, a monomer selected from the group consisting of a-olefins containing from 2 to 10 carbon atoms, vinyl esters of alkanoic acids containing from 3 to 10 carbon atoms, ethyl and methyl esters of acrylic and methacrylic acids, acrylonitrile, methacrylonitrile, styrene and vinyl chloride; and

2. a chelate ester of orthotitanic acid having the forwherein n is an integer of 2 or 3, R is a C to C alkyl, alkenyl, substituted alkyl or substituted alkenyl group, R is a C to C alkyl, alkoxy, alkenyl or alkenoxy group, R is a C, to C alkyl or alkenyl group or a C to C aryl group and R is hydrogen or a C to C alkyl or alkenyl group, and R and R may be combined as an ethylene or a trimethylene group.

The invention further provides a process for preparing pressure-sensitive resin solutions with improved viscosity and flow and a process for coating them as films on substrates to provide articles of manufacture comprising films of pressure-sensitive interpolymer containing the above-described chelate esters of orthotitanic acid.

DESCRIPTION OF THE INVENTION The practice of the present invention involves the preparation of the interpolymer which is then formulated with the chelate ester of orthotitanic acid in a suitable organic solvent. The solution is cast on a sub- I strate and the resulting film is dried and cured to a hydroxypropyl acrylate and methacrylate and 3- hydroxypropyl acrylate and methacrylate, and bis(2-hydroxyethyl)fumarate and maleate. Monomers containing carboxyl groups are exemplified by acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, and the like, maleic acid, fumaric acid, citraconic acid, itaconic acid, and the like, and the alkyl monoesters of maleic acid, fumaric acid, citraconic acid and itaconic acid in which the alkyl group contains from 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl and octyl maleates and the like. Preferred acid monomers include acrylic acid and methacrylic acid. Monomers containing enolizable keto groups include N,N- diacetonylacrylamide and N,N-diacetonylmethacrylamide. The amount of group A monomer in the interpolymer is generally in the range of 0.5 to 20 weight per cent of the interpolymer, and is preferably in the range of l to per cent for adequate crosslinking potential without excessive solution viscosity.

Group B monomers include the esters of acrylic and methacrylic acid containing from 6 to 20 carbon atoms. Preferred esters contain branched chain alkyl groups such as isobutyl acrylate, 2-ethylhexyl acrylate and 2- ethylhexyl methacrylate. The pressure-sensitive resin need only contain monomers from groups A and B. However, Optionally, monomers from Group C may also be present. Group C includes a-olefins containing from 2 to 10 carbon atoms, vinyl esters of alkanoic acids containing 3 to 10 carbon atoms such as vinyl acetate and vinyl octoate, ethyl and methyl esters of acrylic and methacrylic acids, acrylonitrile, methacrylonitrile, styrene and vinyl chloride.

The ratio of monomers in the interpolymer is selected so that the glass transition temperature is in the range of to 75C. A suitable ratio is conventionally calculated from the equation:

ill I where T,, is the glass transition temperature of the interpolymer expressed as degrees Kelvin, T T etc. are the glass transition temperatures of the homopolymers of the respective comonomers and W W etc. are the weight fractions of comonomers required for a specific glass transition temperature of the interpolymer. Glass transition temperatures are determined experimentally by conventional methods such as by means of the du- Pont Differential Thermal Analyzer.

The weight average molecular weight of the interpolymer is in the range of 10,000 to 500,000, corresponding to a relative viscosity in the range of 1.3 to 8.0 measured on a solution of 2 grams of interpolymer per deciliter of benzene. The preferred molecular weight range is from 20,000 to 300,000, providing adequate cohesive strength to the interpolymer without excessive solution viscosity.

The interpolymers are conveniently prepared by organic solvent polymerization techniques involving in some cases delayed addition of monomer when there is a great disparity between reactivity ratios as for example between the reactivity ratios of vinyl acetate and acrylate monomers. The time interval for the delayed addition may range from about 60 to about 600 minutes and longer. The techniques in general, involve the polymerization of the respective monomer mixtures in Suitable organic solvents, the polymerization being initiated by heat activated free radical initiators.

The choice of solvents for the interpolymer used in the practice of this invention is governed by the solubility requirements of the monomers and the resulting interpolymers in that both the monomers and the resulting interpolymers should be soluble in the selected solvent or mixtures of solvents. A further requirement is that the interpolymer solution should contain less than 3 per cent water by weight, based on the total weight of the solvent, in order to avoid adverse interference with the metal alkoxide component. More preferably, the interpolymer solution should contain less than 2 per cent water by weight.

Examples of suitable solvents for the interpolymers include aromatic solvents such as benzene, toluene, xylene, etc. Suitable aliphatic solvents include esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, etc.; ketones such as methyl ethyl ketone, acetone, etc.; aliphatic hydrocarbons such as hexane, pentane, etc. Especially useful are mixtures of the foregoing.

The polymer systems of this invention may also be prepared in mass or non-aqueous dispersion type polymerization processes as are well known to those skilled in the art. However, solution polymerization processes are preferred.

Polymerization initiators suitable for the preparation of the special interpolymers of this invention include organic peroxides, such as tert-butyl hydroperoxide, di-tert-butylperoxide, cumene'hydroperoxide, di-cumyl peroxide, benzoyl peroxide and the like. Equally suitable are organic peroxygen compounds such as tertbutyl peracetate, acetate, tert-butyl perbenzoate, ditert-butyl perphthalate; other initiators would include a-azo-di-isobutyronitrile, -azo-di-isobutytronitrile, ultraviolet light, gamma radiation, etc.

The following Examples 1 to 13 illustrate the preparation formulation and testing of the special interpolymers which are to be used in the practice of this invention and are not to be construed as limitations thereof. All parts and percentages are by weight unless otherwise specified and the expressions polymer and interpolymer are used interchangeably.

PREPARATION OF INTERPOLYMERS EXAMPLE 1 This Example illustrates the preparation of an interpolymer comprising 50.5 parts 2-ethylhexyl acrylate, 45 parts methyl acrylate and 4.5 parts 2-hydroxyethyl acrylate.

The polymer is prepared under reflux conditions in a kettle equipped with a stirrer, condenser, holding tanks and pumps.

AMOUNT OF INGREDIENTS, Parts by Weight Charges 1 and 2 are made at uniform rates over the 1% hour period after the initial charge reaches reflux. After 6 /2 hours of reflux, the batch is cooled and charge 3 is added. The solids content is 41.0 per cent.

wherein n is an integer of 2 or 3, R, is a C to C alkyl, alkenyl, substituted alkyl or substituted alkenyl group, R is a C to' C alkyl, alkoxy, alkenyl or alkenoxy group, R is a C to C alkyl or alkenyl group or a C The Brookfield viscosity is 3,000 cps. The relative vis- 5 t C aryl group and R is hydrogen or a C to C alkyl cosity, determined with a solution of 2 grams of resin or lk l group, d R d R ma be combined as in 100 benzene is an ethylene or a trimethylene group.

' venti nal EXAMPLES 2 to 1 1 The chelate esters are prepared by con 0 methods such as the addition of the appropriate chelat- The general procedure of Example 1 is followed ex- 10 ing agent to an alkyl or alkenyl titanate wherein the cept that different monomers and monomer ratios are lk l o alken l grou contains 2 to 10 carbon atoms. used in order to illustrate a variety of interpolymers Among h h l i agents whi h an be used are, for us d In the p i of this mvemionexample, acetylacetone, propionylacetone, benzoy- TABLE 1 lacetone, 1,3-cyclopentandione, 1,3-cyclohexandione, alkyl acetoacetates, such as ethyl acetoacetate, and the COMPOSITIONS OF INTERPOLYMERS alkyl and alkenyl substituted derivatives of these dike- PREPARED IN EXAMPLES 1 to 11 tones and acetoacetates. Thus, where acetylacetone 1s Ex Monomeric Components weight Ratio used as the chelating agent the R and R groups are methyl and the R group is hydrogen. The chelating l EHA/MA/HEA /4 /4- agents may be reacted with the lower alkyl or alkenyl 5 titanate in a molar ratio ranging from 1:1 to 2:1. The 4 EHA/MA/AA 61/33/62 preferred ratio is about 2:1 so that, for example, when 2 gljhxgi acetylacetone is used, a dialkoxy titanium diacetylace- 7 VAc/EHA/HPA 45/50/5 tonate is obtained. The alkanol generated by the reac- 3 VAC/EHA/HEMA 35/60/5 tion may be distilled. Alternatively, it may be allowed 9 VAc/EHA/HEF 40/55/5 H 10 AN/EHA/HEMA 25/705 to remain so that the product of reaction is essentia y H V l/EHA/HEMA a solution of chelate ester in alkanol. The preferred LEGEND chelate esters are dialkoxy titanium diacetylacetonates, EHA zcthyihcxyl acrylmc 30 dialkyl titanium di(1,3cyclopentandionates) and MA methyl acrylate dialkoxy titanium di(1,3-cyclohexand1onates). HEA zfhydmxyelhyl acrylate The amount of chelate ester used in a given resin so- VAc vinyl acetate AA acrylic acid lution will depend on the type of reactive group in the 3g? gtyg yp gp y iay t interpolymer, the molecular weight of the interpoly- C e HEF j ffigf g mer, the concentration of interpolymer in the solution, AN acrylonitrilc the composition of the solvent and the degree of cross- VCl vinyl chloride iBA isohmyl acrylme linking desired in the pressure-sensitive resin after it has been cast from solution. As little as 0.01 parts by TABLE 2 SOLUTION PROPERTIES OF INTERPOLYMERS OF EXAMPLES 1 to 11 SOLVENT, Weight Relative Ex. Ethyl Acetate Toluene Hexanc iPrOH EtOH Solids, Viscosity, cps. Viscosity FORMULATION OF RESIN SOLUTIONS WITH CHELATE ESTERS OF ORTHOTITANIC ACID (R O), Ti

weight of the chelate ester per 100 parts by weight of interpolymer can give a significant effect on the cohe sive strength of the polymer as measured by the creep resistance. As much as 4.0 parts by weight of the chelate ester per 100 parts by weight of interpolymer can be used especially with lower molecular weight inter polymers and/or lower concentrations of functional groups. However, the preferred range is between 0.1 and 1.0 parts by weight per 100 parts of interpolymer to achieve an appreciable degree of crosslinking without an undesirable increase in the viscosity of the resin solution.

Unlike the lower alkyl titanates, the chelate esters of orthotitanic acid may be added to the interpolymer solutions in the absence of highly polar solvents such as the lower alcohols and much higher concentrations of and speed. Viscosity stability is determined from viscosity measurements over a 7 day period.

The stringiness index (S.I.) is determined by immersing a platinum surface tension ring of 3.6 cm diameter,

resin and chelate ester can be achieved in the solution 1 inch below the surface of the pressure-sensitive resin without excessive viscosity, stringiness or gelling. Howsolution contained in a3 inch diameter jar. The ring is ever, it may Still be advantageous to include a lower mounted in the jaw of an Instron Test Machine and is ebhbi in the resin Solution to increase e solubihty P withdrawn from the solution by allowing the crosshead rametet of the Solvent, Particularly when the Substrate upon which the jar rests to descend at a rate of 5 inches to be coated can be swollen by the less polar solvents per minute. The tensile force exerted on the ring i which are conventionally used in the solution interpolyd d b means of the A cell on the chart set at 10 merizatioh P Apart from the Optional use of 3 grams full scale and moving at 5 inches per minute. The lower alcohol, conventional solvents and solvent blends stringiness i d i measured f the peak f i are selected for use in the pressure-sensitive resin solumum extensional f r to the f il point f h 1 tions of this invention on the basis of the solubility regating Curtain f l ti Five measurements are made quirements of the resin and the nature Of the Substrate in rapid succession. The arithmetic average expressed IS to be coated. The solids content of the resin in inches isthe stringiness index In genera] a stringi Solutions can be Varied between 10 P ceht and 60 P ness index of less than 0.30 inch indicates that a resin cent for application to the Substrate The Preferred solution has good flow properties and that the solution ebheehtratieh is between and P eeht- 20 will not form strings on conventional high-speed roll EVALUATION OF PRESSURE-SENSITIVE RESIN coaters at normal speeds of operation. The tendency of SOLUTIONS a pressure-sensitive resin solution to develop stringi- In the evaluation of pressure-sensitive resin solutions is determined y measurement of the stringiness containing esters of orthotitanic acid, the solutions are 25 index Over a 7 y pe formulated to 32 weight per cent solids. The esters of The data for Viscosity and stringiness index of the i orthotitanic acid are added in ethanol solution gradu- 'p y Solutions of Examples formulated with ally with stirring to the pressure-sensitive resin solution, Various esters of Orthotitahie acid are Presented in a h amount f h l b i 25 i ht per t f th bles 3 and 4. The solids content of the solutions is 32 total Solvent i h fi l l i 30 per cent. Ethanol forms 25 per cent of the solvent. In The solutions are subjected to determination of visthe Tables, TBT signifies tetrabutyl tltahate and TAA cosity and -stringiness index. Viscosity is determined signifies p p y titanium d1aeetylacetonate at 20C. by the conventional method using a Brookfield which is formed y reaction of 2 moles of aeetylaee' Model LVF Viscometer and the appropriate spindle t With 1 mole of p py titahate- TABLE 3 EFFECT OF TITANATE TYPE ON SOLUTION VISCOSlTIES(viscosities in cps.)

RESIN Titanate Example 1 Example 2 Example 3 Example 4 Concentration. grams Aged Aged Aged Ag per 100 g. resin Type Initial 1 week Initial 1 week Initial 1 week Initial l W( 0 none 800 850 195 1 375 380 0.2 TBT 1,170 1,140 270 280 535 560 TAA 810 840 235 240 415 410 0.4 TBT 1,920 1,800 470 500 1,1 10 1,200 Gel Gel TAA 870 900 300 345 450 460 7,700 14,000 0.6 TBT Gel Gel 1,130 1,350 2,550* 3,000* Gel Gel TAA 940 1,000 250 250 455 480 9,000 18,000

Very ropy, stringy; no! coalablc.

TABLE 4 EFFECT ON TITANATE TYPE ON STRINGINESS INDEX in inches) RESIN Titanate Example 1 Example 2 Example 3 Concentration, grams Aged Aged Aged per g. resin Type Initial 1 week Initial 1 week Initial 1 week 0 None 0.18 0.21 0.23 0.19 0.13 0.14 0.2 TBT 0.22 0.25 0.21 0.30 0.14 0.17 TAA 0.18 0.21 0.20 0.29 0.18 0.18 0.4 TBT 0.35 0.27 0.37 0.41 0.21 0.20 TAA 0.20 0.19 0.18 0.26 0.18 0.18 0.6 TBT 0.39 0.53 0.64 0.72 TAA 0.20 0.22 0.22 0.27 0.18 0.18

Data for stringiness index of interpolymer solutions of Examples 3 and 6 through 1 l formulated with various chelate esters of orthotitanic acid are presented in Table 5. The solids content of the solutions is 30 per cent. Ethanol forms 25 per cent of the solvent. The concentration of ehelate ester of titanium is 0.4 parts per 100 parts by weight of resin.

EVALUATION OF PRESSURE-SENSITIVE RESINS The pressure-sensitive resin solutions listed in Table 3 are cast on silicone release paper, and the cast films are dried at room temperature, then at 90C. for 2 minutes. The (0.8 mil thickness) films are cooled to room temperature and applied to polyvinyl chloride film (Ultron Polyvinyl Chloride UL-58 Film, 3 mil thick, supplied by Monsanto Company). The laminate is cut into 1 inch strips. The strips are conditioned at 70F. and 50% relative humidity for 24 hours. The release paper is removed and the strips are applied to steel panels (ASTM 1000-65) with a Pressure-Sensitive Tape Council roller. Peel strength is determined on an Instron Test Machine by peeling the strip at a 180 angle and at a rate of 6 inches per minute from the steel panel. Green" strength is gauged by comparing the peel strength of the bond 20 minutes after formation and 24 hours after formation. Data are presented in Table 6.

TABLE 5 STRINGINESS INDEX OF INTERPOLYMER SOLUTIONS CONTAINING CHELATE ESTERS OF ORTHOTITANIC ACID TITANIUM CHELATE ESTER Resin Stringiness Ex. n R Chelating Agent Index( in.)

3 2 isopropyl acetylacetone 03 6 3 iso-propyl ucetylacetone 03 7 2 octyl benzoylacetone 03 8 2 butyl I ,3-cyclohexanedione 03 9 2 octyl I .3-cyclopentanedione 0.3 l0 2 butyl ethyl acetoacctate 03 I l 2 iso-propyl acetylacetone 0.3

TABLE 6 product of E. I. duPont de Nemours and Company) and a polished stainless steel bar. The Mylar strip is loaded with a one-pound weight. The bond is held in a vertical plane at 70F. and relative humidity and the time in hours for failure after application of the load is determined. The data are presented in Table 7.

TABLE 7 CREEP RESISTANCE OF PRESSURE SENSITIVE RESINS (hours to failure) Note that at low concentrations of titanate ester, the initial creep resistance is roughly the same for resins containing tetrabutyl titanate and those containing diisopropoxy titanium diacetylacetonate; but at higher concentrations, the creep resistance improves to a higher level for TAA formulations than for the TBT systems. An exception is the Example 2 system for which TBT may be a more efficient crosslinker.

While the present invention has been described with particular reference to certain specific embodiments thereof, it will be understood that certain changes, substitutions and modifications may be made therein without departing from the scope thereof. This invention also contemplates the use of fillers, extenders, stabilizers, antioxidants, plasticizers, tackifiers, flow control agents, adhesion promoters, dyes, etc. in the pressuresensitive resin solutions and the pressure-sensitive resins of this invention.

The compositions of the present invention may be used as the adhesive component in pressure-sensitive PEEL STRENGTH OF PRESSURE-SENSITIVE RESINS (pounds per inch width) RESIN Titanate Example I Example 2 Example 3 Concentration, grams per I00 g. resin Type 20 min. 24 hr. 20 min. 24 hr. 20 min. 24 hr.

0 none 3.8 4.0 5.0 8.6,? 4.2 4.7 0.2 TBT 3.3 4.0 4.0 7.0,? 3.9 4.4 TAA 3.4 3.8 3.7 7.5,.* 3.6 4.6 0.4 TBT 3.0 3.9 3.1 4.8 3.7 4.2 TAA 3.0 4.2 3.0 5.5 3.2 4.2 0.6 TBT 2.5 4.4

TAA 3.0 3.5 2.7 4.5 2.9 4.0

Subscript "c" denotes cohesive splitting of the film.

tapes, films and foams. They adhere well to resin surfaces such as plasticized poly(vinyl chloride) Mylar, cellulose acetate, nylon, polyethylene and polypropylene, as well as to paper, metal and painted surfaces. They are especially useful as the adhesive component of decorative vinyl sheets and decals, conferring excellent shrink resistance to vinyl film. Their excellent tack retention, creep resistance and resistance to plasticizer migration make them useful as adhesives for vinyl foam and tiles. Their outstanding tack, wetting and holding power may be used to advantage in transfer adhesive applications.

Articles of manufacture such as tapes, decals, decorative vinyl sheets and transfer films containing the pressure-sensitive resin composition of the present invention are prepared by coating the resin on the appropriate substrate by conventional coating methods. Such articles conventionally include a release paper for temporary protection of the adhesive film until the adhesive bond is made. The thickness of the adhesive film is generally in the range of 0.2 to mil.

Application of the film to the substrate is conventionally carried out on roll coaters such as reverse roll and gravure roll coaters. The resin solution viscosity is adjusted to between 25 and 5,000 centipoises with higher viscosities within the range preferred for reverse roll coating and lower viscosities within the range preferred for gravure coating. The coatings are applied to the substrate moving through the rolls at a rate of between feet per minute and 1,000 feet per minute.

EXAMPLE 12 This Example is set forth to compare the performance of a resin solution formulated with tetrabutyl titanate with a resin solution formulated with diisopropoxy titanium diacetylacetonate in reverse roll application to a poly(vinyl chloride) substrate at a rate of 50 ft./min.

Polymer solutions made according to Example l are diluted to 30 per cent solids and formulated with 0.5 parts tetrabutyl titanate or diisopropoxy titanium diacetylacetonate per 100 parts of resin. The levels of titanate compound are selected to give the desired cohesive strength in the dried films. The TBT solution had a Stringiness Index of about 0.45 and gives poor coatings of rough surface texture and uneven thickness. A large number of strings are observed between the application roll and the substrate during the coating operation. These coatings are judged unsuitable for commercial use. The TAA solution has a Stringiness Index of about 0.20 and gives smooth coatings of uniform thickness. These films are judged satisfactory for commercial use.

What is claimed is:

l. A process of manufacture of an article coated with a film of pressure-sensitive resin comprising:

A. preparing an organic solvent solution containing an interpolymer comprising:

1. between 0.5 and weight percent of at least one monomer containing an enolizable keto group selected from the group consisting of N,N- diacetonylacrylamide and N,N-diacetonylmethacrylamide; and

2. at least one monomer selected from the group consisting of esters of acrylic acid and methacrylic acid containing from 6 to 20 carbon atoms;

wherein the interpolymer has a weight average molecular weight in the range of 10,000 to 500,000 and a glass transition temperature in the range of 15 to C.; B. adding an organic solvent solution of a chelate ester of orthotitanic acid to obtain a solution of the interpolymer containing between 0.01 and 4.0 parts of the chelate ester per parts of interpolymer with a Stringiness index of less than 0.3 inches and a viscosity in the range of 25 to 5000 cps. at 20C., wherein the chelate ester is represented by the formula:

wherein n is an integer of 2 or 3, R is a C to C alkyl, alkenyl, substituted alkyl or substituted alkenyl group, R is a C to C alkyl, alkoxy, alkenyl or alkenoxy group, R is a C to C alkyl or alkenyl group or a C to C aryl group and R is hydrogen or a C alkyl or alkenyl group, and R and R may be combined as an ethcyclohexandione, alkyl acetoacetates, and their C to- C alkyl and alkenyl substituted derivatives, the mole ratio of tetraalkyl or tetraalkenyl titanate to enolizable keto compound being in the range of 1:1 to 1:2.

3. The process of claim 2 wherein the enolizable keto compound is acetylacetone.

4. The process of claim 1 wherein the concentration of chelate ester of orthotitanic acid is between 0.1 and 1.0 parts by weight per 100 parts by weight of interpolymer.

5. The process of claim 1 wherein the article is a film of plasticized polyvinyl chloride, polyethylene terephthalate, cellulose acetate, nylon, polyethylene, polypropylene, paper or silicone coated paper.

6. The process of claim 1 wherein the interpolymer further contains a monomer selected from the group consisting of a-olefins containing from 2 to 10 carbon atoms, vinyl esters of alkanoic acids containing from 3 to 10 carbon atoms, ethyl and methyl esters of acrylic and methacrylic acids, acrylonitrile, methacrylonitrile,

styrene, and vinyl chloride. 

1. A PROCESS OF MANUFACTURE OF AN ARTICLE COATED WITH A FILM OF PRESSURE-SENSITIVE RESIN COMPRISING: A. PREPARING AN ORGANIC SOLVENT SOLUTION CONTAINING AN INTERPOLYMER COMPRISING:
 1. BETWEEN 0.5 AND 20 WEIGHT PERCENT OF AT LEAST ONE MONOMER CONTAINING AN ENOLIZABLE KETO GROUP SELECTED FROM THE GROUP CONSISTING OF N,N-DIACETONYLACRYLAMIDE AND N,N-DIACETONYLACRYLAMIDE, AND
 2. AT LEAST ONE MONOMER SELECTED FROM THE GROUP CONSISTING OF ESTERS OF ACRYLIC ACID AND METHACRYLIC ACID CONTAINING FROM 6 TO 20 CARBON ATOMS, WHEREIN THE INTERPOLYMER HAS A WEIGHT AVERAGE MOLECULAR WEIGHT IN THE AVERAGE OF 10,000 TO 500,000 AND A GLASS TRANSITION TEMPERATURE IN THE RANGE OF -15* TO -75*C., B. ADDING AN ORGANIC SOLVENT SOLUTION OF A CHELATE ESTER OF ORTHOTITANIC ACID TO OBTAIN A SOLUTION OF THE INTERPOLYMER CONTAINING BETWEEN 0.01 AND 4.0 PARTS OF THE CHELATE ESTER PER 100 PARTS OF INTERPOLYMER WITH A STRINGINESS INDEX OF LESS THAN 0.3 INCHES AND A VISCOSITY IN THE RANGE OF 25 TO 5000 CPS. AT 20*C., WHEREIN THE CHELATE ESTER IS REPRESENTED BY THE FORMULA:
 2. at least one monomer selected from the group consisting of esters of acrylic acid and methacrylic acid containing from 6 to 20 carbon atoms; wherein the interpolymer has a weight average molecular weight in the range of 10,000 to 500,000 and a glass transition temperature in the range of -15* to -75*C.; B. adding an organic solvent solution of a chelate ester oF orthotitanic acid to obtain a solution of the interpolymer containing between 0.01 and 4.0 parts of the chelate ester per 100 parts of interpolymer with a stringiness index of less than 0.3 inches and a viscosity in the range of 25 to 5000 cps. at 20*C., wherein the chelate ester is represented by the formula:
 2. The process of claim 1 wherein the chelate ester is the reaction product of a tetraalkyl or tetraalkenyl titanate wherein the alkyl or alkenyl group contains 2 to 10 carbon atoms, and an enolizable keto compound selected from the group consisting of acetylacetone, benzoylacetone, 1,3-cyclopentandione, 1,3-cyclohexandione, alkyl acetoacetates, and their C1 to C6 alkyl and alkenyl substituted derivatives, the mole ratio of tetraalkyl or tetraalkenyl titanate to enolizable keto compound being in the range of 1:1 to 1:2.
 3. The process of claim 2 wherein the enolizable keto compound is acetylacetone.
 4. The process of claim 1 wherein the concentration of chelate ester of orthotitanic acid is between 0.1 and 1.0 parts by weight per 100 parts by weight of interpolymer.
 5. The process of claim 1 wherein the article is a film of plasticized polyvinyl chloride, polyethylene terephthalate, cellulose acetate, nylon, polyethylene, polypropylene, paper or silicone coated paper.
 6. The process of claim 1 wherein the interpolymer further contains a monomer selected from the group consisting of Alpha -olefins containing from 2 to 10 carbon atoms, vinyl esters of alkanoic acids containing from 3 to 10 carbon atoms, ethyl and methyl esters of acrylic and methacrylic acids, acrylonitrile, methacrylonitrile, styrene, and vinyl chloride. 